JPH0328206A - Manufacture of vinyledene fluoride polymer and use of vinyledene fluoride polymer for blending paints - Google Patents
Manufacture of vinyledene fluoride polymer and use of vinyledene fluoride polymer for blending paintsInfo
- Publication number
- JPH0328206A JPH0328206A JP2065514A JP6551490A JPH0328206A JP H0328206 A JPH0328206 A JP H0328206A JP 2065514 A JP2065514 A JP 2065514A JP 6551490 A JP6551490 A JP 6551490A JP H0328206 A JPH0328206 A JP H0328206A
- Authority
- JP
- Japan
- Prior art keywords
- vinylidene fluoride
- fluoride polymer
- producing
- polymerization
- initiator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 30
- 239000003973 paint Substances 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title description 4
- 238000002156 mixing Methods 0.000 title 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000003999 initiator Substances 0.000 claims abstract description 13
- -1 alkyl acetate Chemical compound 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 239000012736 aqueous medium Substances 0.000 claims abstract description 4
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 238000009472 formulation Methods 0.000 claims description 13
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical class [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 7
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 5
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 4
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 12
- 239000002033 PVDF binder Substances 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 229920001959 vinylidene polymer Polymers 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 244000062793 Sorghum vulgare Species 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 235000019713 millet Nutrition 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000004976 peroxydisulfates Chemical class 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/16—Homopolymers or copolymers of vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F114/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F114/18—Monomers containing fluorine
- C08F114/22—Vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/18—Monomers containing fluorine
- C08F14/22—Vinylidene fluoride
Abstract
Description
【発明の詳細な説明】
（発明の産業上の利用分野）
本発明は、フッ化ビニリデンポリマーの製造方法、並び
に塗料、特に金属シートのプレラフカー塗に意図される
塗料の配合のための生成フッ化ビニリデンポリマーの使
用に関する。DETAILED DESCRIPTION OF THE INVENTION Industrial Application of the Invention The present invention relates to a process for producing vinylidene fluoride polymers and the resulting fluoride polymers for the formulation of coatings, especially those intended for pre-rough car coating of metal sheets. Concerning the use of vinylidene polymers.
（従来の技術）
空中薬剤及び腐蝕に耐える塗料及び接着被覆物の配合の
ため、特に、金属シートのプレラソカー塗、即ちしばし
ば“コイル被覆”という用語により称される操作に意図
される塗料の配合のため、フッ化ビニリデンポリマーを
使用することが知られている。この種の塗料は、一般に
約２０ミクロンを超えない厚さの非常に薄い被覆物とし
て塗布される。水性乳化重合により得られたフッ化ビニ
リデンポリマーは、通常フッ化ビニリデンポリマーをベ
ースとするこのような塗料の配合に必要とされる．
ヅードドイチェ・カルクスティソクストソフベルケ（Ｓ
ｉｉｄｄｅｕｔｓｃｈｅ Ｋａｌｋｓｔｉｃｋｓｔｏｆ
ｆ−Ｗｅｒｋｅ）ＡＧ名義のフランス特許ＦＲ−Ａ−２
．０５ ６，６３ ６号には、金属の保護を目的とする
オルガノゾルヮニスの配合に適した、約０．２Ｇクロン
の平均の大きさを有する微細（一次）粒子としてのポリ
フッ化ビニリデンの製造方法が記載されている．この方
法は、開始剤としてペルオキシジスルフェートを使用し
て、乳化剤の不在下で、水性媒体中でフッ化ビニリデン
を重合することからなる．この方法は、その簡素化のた
め、及びその使用に必要とされる少数の重合成分（本質
的に、水、モノマー及び水溶性開始剤）のため、特に魅
力的である．それにもかかわらず、上記の従来技術の方
法により得られたボリフソ化ビニリデンは、低い光沢の
塗料及び被覆物を生じることがわかった。塗料、特に金
属シートのプレラッカー塗のための塗料の分野に於ける
多くの適用に際し、有用な高光沢塗料を有することが、
主として重要である。BACKGROUND OF THE INVENTION For the formulation of paints and adhesive coatings resistant to airborne chemicals and corrosion, in particular the formulation of coatings intended for pre-lasocar coating of metal sheets, an operation often referred to by the term "coil coating". Therefore, it is known to use vinylidene fluoride polymer. Paints of this type are applied as very thin coatings, generally no more than about 20 microns thick. Vinylidene fluoride polymers obtained by aqueous emulsion polymerization are usually required for the formulation of such paints based on vinylidene fluoride polymers. S
iiddeutsche Kalkstickstof
f-Werke) AG's French patent FR-A-2
．． No. 05 6,63 No. 6 describes the production of polyvinylidene fluoride as fine (primary) particles with an average size of about 0.2 Gkr, suitable for the formulation of organosolvanis for the protection of metals. The method is described. This method consists of polymerizing vinylidene fluoride in an aqueous medium in the absence of emulsifiers using peroxydisulfate as an initiator. This method is particularly attractive because of its simplicity and because of the small number of polymerization components (essentially water, monomer and water-soluble initiator) required for its use. Nevertheless, it has been found that the polyphthovinylidene obtained by the above-mentioned prior art process results in paints and coatings of low gloss. For many applications in the field of coatings, especially coatings for pre-lacquering metal sheets, it is desirable to have a high gloss coating that is useful.
Primarily important.
（発明が解決しようとする課題〉
本発明の目的は、改良された光沢をもつ塗料の配合に使
用し得るフッ化ビニリデンボリマ−の改良された製造方
法を提供することである。OBJECTS OF THE INVENTION It is an object of the present invention to provide an improved process for producing vinylidene fluoride polymers that can be used in the formulation of paints with improved gloss.
（課題を解決するための手段）
この目的のため、本発明は、乳化剤の不在下で開始剤と
してベルオキシジスルフェートを使用して水性媒体中で
フッ化ビニリデンの非連続的重合によるフッ化ビニリデ
ンポリマーの製造方法であって、
連鎖調節剤が重合用の初期の水性仕込み液に導入され、
上記の連鎖調節剤が酢酸アルキル（そのアルキル基は１
〜３個の炭素原子を含む）から選ばれることを特徴とす
る、上記のフッ化ビニリデンポリマーの製造方法に関す
る。SUMMARY OF THE INVENTION To this end, the present invention provides fluorination by discontinuous polymerization of vinylidene fluoride in an aqueous medium using peroxydisulfate as an initiator in the absence of emulsifiers. A method for producing vinylidene polymers, comprising: introducing a chain regulator into an initial aqueous charge for polymerization;
The above chain regulator is alkyl acetate (the alkyl group is 1
to 3 carbon atoms).
本発明の方法に使用し得る酢酸アルキルの例として、酢
酸メチル、酢酸エチル、酢酸プロビル及び酢酸イソプロ
ビルが挙げられる。特に非常に好ましい酢酸アルキルは
酢酸エチルである。Examples of alkyl acetates that can be used in the method of the invention include methyl acetate, ethyl acetate, probyl acetate and isopropyl acetate. A particularly highly preferred alkyl acetate is ethyl acetate.
重合用の初期の水性仕込み液中で全ての連鎖調節剤を使
用することが、本発明の範囲内で、必須である。It is essential within the scope of the present invention to use all chain regulators in the initial aqueous charge for polymerization.
使用される連鎖調節剤の量は、特に重要ではない。それ
は、勿論、分子量に依存し、それ故、ポリマーに付与す
ることが意図される極限粘度に依存する。一般に、使用
されるモノマーに対して約０． ５〜３重量％の調節剤
が使用される。この濃度範囲内で、調節剤の量は、重合
条件及び目的とされる結果の関数として、実験により有
利に選ばれる。一般に好ましい濃度範囲は、使用される
モノマーに対して１〜２％の調節剤である。この濃度範
囲に於いて、ジメチルホルムアごド中２５℃で測定した
極限粘度が約０．１２〜０．００５ｇ／ｌであるボリフ
ッ化ビニリデンが生戒される。The amount of chain regulator used is not particularly critical. It, of course, depends on the molecular weight and therefore on the intrinsic viscosity that is intended to be imparted to the polymer. Generally, about 0.0% based on the monomers used. 5-3% by weight of regulator is used. Within this concentration range, the amount of regulator is advantageously chosen experimentally as a function of the polymerization conditions and the desired result. A generally preferred concentration range is 1-2% modifier based on the monomers used. In this concentration range, polyvinylidene fluoride having an intrinsic viscosity of about 0.12 to 0.005 g/l, measured at 25 DEG C. in dimethylformado, is acceptable.
本発明の方法に於いて、重合はベルオキシジスルフェー
ト型の開始剤により開始される。このようなペルオキシ
ジスルフェートの例として、ナトリウム及びカリウムの
如きアルカリ金属のペルオキシジスルフェート、及びア
ンモニウムペルオキシジスルフェートが挙げられる。ア
ンモニウムペルオキシジスルフェートが使用されること
が好ましい。In the process of the invention, polymerization is initiated by a peroxydisulfate type initiator. Examples of such peroxydisulfates include alkali metal peroxydisulfates such as sodium and potassium, and ammonium peroxydisulfate. Preferably ammonium peroxydisulfate is used.
重合に使用される開始剤の量は、或る制限内で変化し得
る。それにもかかわらず、水性相１ｊ２当り少なくとも
０．００５ｇであり、かつ水性相ｌｌ当り０．５ｇ以下
を使用することが推奨される。開始剤濃度は、水性相１
ｌ当り約０．０３〜０．２ｇであることが好ましい。開
始剤は、初期の水性仕込み液中に全部または一部存在し
てもよい。本発明の好ましい実施態様によれば、全ての
べルオキシジスルフエートは重合の過程中に仕込み液中
に次第に導入される．
重合温度は重要ではない。それにもかかわらず、重合温
度は約８０〜９５℃の範囲にあることが有利である。上
記の温度範囲に於いて、フッ化ビニリデンは、その臨界
温度（３０．１”Ｃ）より上にあり、その結果操作圧力
は本質的に温度に依存し、重合容器中に存在するモノマ
ーの量に依存する。The amount of initiator used in the polymerization can vary within certain limits. Nevertheless, it is recommended to use at least 0.005 g per liter of aqueous phase and not more than 0.5 g per liter of aqueous phase. Initiator concentration is aqueous phase 1
Preferably, it is about 0.03 to 0.2 g per liter. The initiator may be present in whole or in part in the initial aqueous charge. According to a preferred embodiment of the invention, all the peroxydisulfate is gradually introduced into the charge during the course of the polymerization. Polymerization temperature is not critical. Nevertheless, it is advantageous for the polymerization temperature to be in the range of about 80-95°C. In the above temperature range, vinylidene fluoride is above its critical temperature (30.1"C), so that the operating pressure is essentially temperature dependent and the amount of monomer present in the polymerization vessel. Depends on.
処理効率の理由のため、重合圧力は２０バールより高い
ことが有利であり、約３０〜４５バールであることが好
ましい．それは、フッ化ビニリデンの次第の導入により
調節され、保たれる。導入されるフッ化ビニリデンの合
計量は、一般に水ｌ重量部に対し０．２２重量部を越え
ない。For process efficiency reasons, the polymerization pressure is advantageously higher than 20 bar, preferably about 30 to 45 bar. It is regulated and maintained by the gradual introduction of vinylidene fluoride. The total amount of vinylidene fluoride introduced generally does not exceed 0.22 parts by weight per part by weight of water.
それ故、本発明の方法の好ましい実施態様は、重合用の
初期の水性仕込み液中に全ての連鎖調節剤（酢酸アルキ
ル）を導入すること、及び重合の過程中に仕込み液に開
始剤及びフッ化ビニリデンを次第に導入することからな
り、後者の化合物は圧力を選ばれた値に保つのに充分な
量で導入される。Therefore, a preferred embodiment of the process of the invention involves introducing all the chain regulator (alkyl acetate) into the initial aqueous charge for the polymerization and adding initiator and fluoride to the charge during the course of the polymerization. It consists in gradually introducing vinylidene chloride, the latter compound being introduced in an amount sufficient to maintain the pressure at the chosen value.
フッ化ビニリデンの重合は、本発明の範囲内で、フッ化
ビニリデンの単独重合並びにモノマー類と多量、好まし
くは８５モル％より多くのフッ化ビニリデンとの混合物
、例えばフッ化ビニリデンとフッ化ビニル、トリフルオ
ロエチレン、クロロトリフルオ口エチレン、テトラフル
オ口エチレン及びヘキサフルオ口プロピレンの如きその
他のフルオロオレフィンとの混合物との共重合を表わす
ことが意図される。それにもかかわらず、フッ化ビニリ
デンの単独重合が好ましい。Polymerizations of vinylidene fluoride are within the scope of the invention homopolymerizations of vinylidene fluoride as well as mixtures of monomers with large amounts of vinylidene fluoride, preferably more than 85 mol %, such as vinylidene fluoride and vinyl fluoride, It is intended to represent copolymerizations with mixtures with other fluoroolefins such as trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene and hexafluoropropylene. Nevertheless, homopolymerization of vinylidene fluoride is preferred.
重合が終了した時、本発明の方法は、微細なフッ化ビニ
リデンボリマ−（その均一な球形の一次粒子は約０．１
〜０．３ミクロンの平均の大きさを示す）の水性分散液
をもたらす。本発明の方法に従って得られたフッ化ビニ
リデンポリマーは、通常の方法、特に凝固、濾過、洗浄
及び乾燥により、重合媒体から分離される。When the polymerization is completed, the method of the present invention produces fine vinylidene fluoride polymer (the uniform spherical primary particles of which are about 0.1
yielding an aqueous dispersion with an average size of ~0.3 microns). The vinylidene fluoride polymer obtained according to the process of the invention is separated from the polymerization medium by conventional methods, in particular coagulation, filtration, washing and drying.
塗料の配合のためのそれらの使用に鑑みて、凝固物は、
平均の大きさが２０ξクロンより小さい粒子としてフッ
化ビニリデンポリマーを得るように、乾燥中または乾燥
後に、微粉砕される。In view of their use for the formulation of paints, coagulums are
During or after drying, it is milled to obtain the vinylidene fluoride polymer as particles with an average size of less than 20 ξ chromons.
本発明の方法に従って得られたフッ化ビニリデンポリマ
ーは、光沢のある塗料の配合に特に非常に適する。従っ
て、塗料の配合のため、特に金属シートのプレラッカー
塗に意図される塗料の配合のためのこれらのボリマーの
使用は、本発明の別の特徴を形威する。The vinylidene fluoride polymers obtained according to the method of the invention are particularly well suited for the formulation of glossy coatings. The use of these polymers for the formulation of paints, especially those intended for the pre-lacquering of metal sheets, therefore forms another feature of the invention.
ボリフッ化ビニリデン及び分散媒体として使用される有
機溶剤（例えば、ケトン、フタレート及びアセテート）
の他に、ポリフッ化ビニリデンをベースとする塗料の配
合物は、通常、アクリル樹脂の如き樹脂（これはポリフ
ッ化ビニ゛リデンと相溶性であり、しかも上記の溶剤中
にボリフッ化ビニリデンよりも可溶性であり、塗料中の
それの分散を改良することを目的とする）並びに顔料及
び表面活性剤を含む。Polyvinylidene fluoride and organic solvents used as dispersion media (e.g. ketones, phthalates and acetates)
In addition, paint formulations based on polyvinylidene fluoride usually contain resins such as acrylic resins, which are compatible with polyvinylidene fluoride and more soluble than polyvinylidene fluoride in the solvents mentioned above. (with the purpose of improving its dispersion in paints) as well as pigments and surfactants.
以下の実施例は、本発明を説明することを目的とする。The following examples are intended to illustrate the invention.
本発明の例１〜３は、連鎖調節剤としての酢酸エチルの
使用を説明する。参考としての例４は、従来技術の方法
（連鎖調節剤を使用しない）を説明する。Examples 1-3 of the invention illustrate the use of ethyl acetate as a chain regulator. Reference Example 4 describes a prior art method (without chain regulator).
例１〜４は、以下の一般操作に従って行なわれる。Examples 1-4 are performed according to the following general procedure.
粟一金
３５１の容量のステンレス鋼オートクレープに、脱イオ
ン水２５１、続いて添付された表■に特定された量の酢
酸エチルを連続して導入する。オートクレープを閉じ、
窒素でフラッジする．オートクレープの内容物を９２℃
に加熱する．フッ化ビニリデンを注入し、フッ化ビニリ
デンの流量は、オートクレープ中の３５バールの圧力を
確立し保つように調節される。アンモニウムペルオキシ
ジスルフェートを、７７ｃｍ＋’／時間の流量でｌＯｇ
／ｌの水溶液として連続的に注入する。フッ化ビニリデ
ン５．６３ｋｇを注入した後、フッ化ビニリデン及び触
媒の注入をさえぎることにより重合を停止し、ついで加
熱を止め、オートクレープを脱気する。ラテックス（約
０．２ミクロンの一次粒子）を塩化ナトリウムで凝固し
、濾過し、洗浄し、６０℃で乾燥する。ボリフッ化ビニ
リデン５．５ｋｇを回収する。凝固物を、平均粒径が２
０ミクロン未満であるボリマーを得るように、微粉砕す
る。Into a stainless steel autoclave with a capacity of 351 liters of millet metal, 251 liters of deionized water is successively introduced, followed by the amount of ethyl acetate specified in the attached table 3. Close the autoclave;
Flood with nitrogen. The contents of the autoclave were heated to 92°C.
Heat to. Vinylidene fluoride is injected and the flow rate of vinylidene fluoride is adjusted to establish and maintain a pressure of 35 bar in the autoclave. lOg of ammonium peroxydisulfate at a flow rate of 77 cm+'/hr.
Continuously inject as a /l aqueous solution. After injecting 5.63 kg of vinylidene fluoride, the polymerization is stopped by blocking the injection of vinylidene fluoride and catalyst, then heating is stopped and the autoclave is degassed. The latex (approximately 0.2 micron primary particles) is coagulated with sodium chloride, filtered, washed and dried at 60°C. 5.5 kg of polyvinylidene fluoride is recovered. The average particle size of the coagulum is 2.
Grind to obtain a polymer that is less than 0 microns.
例１〜３に従って得られたボリフッ化ビニリデンの極限
粘度（ジメチルホルムアミド中２５℃で測定した〉は、
添付された表Ｉに示される。参考のための例４に従って
、即ち酢酸アルキルの不在下で、得られたボリフッ化ビ
ニリデンの極限粘度は、ジメチルホルムアミド中の不充
分な熔解性のため、測定できなかった。The intrinsic viscosity (measured in dimethylformamide at 25°C) of polyvinylidene fluoride obtained according to Examples 1 to 3 is:
It is shown in attached Table I. According to reference example 4, ie in the absence of alkyl acetate, the intrinsic viscosity of the polyvinylidene fluoride obtained could not be determined due to insufficient solubility in dimethylformamide.
琵一適
例１〜４に従って得られたポリフツ化ビニリデンを、組
或が以下に記載される白色塗料配合中で評価する。The polyvinylidene fluorides obtained according to Biichi Examples 1 to 4 are evaluated in white paint formulations as described below.
ｌ．ｅＬｉ
（＊）ジアセトンアルコール中５％の活性物質を含む溶
液
２．アルくニウムパネルの一ツカー
上記のようにして配合した白色塗料をＯ’． ６ ａ＋
ａ＋の厚さのアル〔ニウムバネルに塗布する。ボリフッ
化ビニリデン被覆物の接着を促進するために、最初にフ
エノキシ樹脂をベースとするブライマー塗料の被覆物を
約５ミクロンの乾燥膜厚で塗布し、パネルを炉中に入れ
、１分を越えない時間〈この場合２９秒）にわたって２
３２℃の温度に達するようにフェノキシ被覆物を硬化す
る。ついで、パネルを炉から取り出し、直ちに冷水浴に
浸す。冷却パネルを乾燥した後、白色塗料を、２０ミク
ロンの乾燥膜厚を得るように、ワイヤースブレグーによ
り塗布し、パネルを炉中に入れ１分を超えない時間（こ
の場合３４秒）にわたって２５４℃の温度に達するよう
に塗料を架橋する。パネルを炉から取り出し、乾燥前に
水浴中で冷却する。l. eLi (*) Solution containing 5% active substance in diacetone alcohol2. For the aluminum panel, apply the white paint formulated as above to O'. 6 a+
Apply to an a+ thickness aluminum panel. To promote adhesion of the polyvinylidene fluoride coating, a coating of phenoxy resin-based brimer paint is first applied to a dry film thickness of approximately 5 microns, and the panel is placed in an oven for no more than 1 minute. 2 over a period of time (29 seconds in this case)
Cure the phenoxy coating to reach a temperature of 32°C. The panels are then removed from the oven and immediately immersed in a cold water bath. After drying the cooled panel, white paint is applied with a wire brush to obtain a dry film thickness of 20 microns, and the panel is placed in an oven for a period of time not exceeding 1 minute (34 seconds in this case) at 254°C. Crosslink the paint to reach a temperature of °C. The panels are removed from the oven and cooled in a water bath before drying.
３．光沢復定
ＩＳＯ規格２，８１３−１９７８に従って、白色塗料の
光沢を、鏡面光沢計（光線の入射角度は６０°に等しい
）により測定する。この評価の原理は、ｌ００の光沢が
割り当てられる磨き黒色ガラス（屈折率１．５６７＞に
より反射される光束に対する、６０″の角度で試料によ
り反射される光束の比を測定することからなる。3. Gloss Restoration The gloss of the white paint is measured according to ISO standard 2,813-1978 with a specular glossmeter (the angle of incidence of the light beam is equal to 60°). The principle of this evaluation consists in measuring the ratio of the luminous flux reflected by the sample at an angle of 60'' to the luminous flux reflected by a polished black glass (refractive index 1.567>, which is assigned a gloss of 100).
１００の光沢が割り当てられる磨き黒色ガラスの光沢に
対する比率（％）で表わされた光沢の評価の結果が、ま
た添付された表■に示される。The results of the gloss evaluation, expressed as a percentage of the gloss of polished black glass, to which a gloss of 100 is assigned, are also shown in the attached table 3.
本発明の例１〜３の結果と参考のための例４の結果との
比較は、連鎖調節剤として酢酸エチルを使用して製造さ
れたポリフッ化ビニリデンで配合された塗料の光沢の著
しい改良を示す。A comparison of the results of Inventive Examples 1-3 with the results of Reference Example 4 shows a significant improvement in the gloss of paints formulated with polyvinylidene fluoride made using ethyl acetate as chain regulator. show.
Claims (1)
フェートを使用して水性媒体中でフッ化ビニリデンの非
連続的重合によるフッ化ビニリデンポリマーの製造方法
であって、連鎖調節剤が重合用の初期の水性仕込み液に
導入され、上記の連鎖調節剤が酢酸アルキル（そのアル
キル基は１〜３個の炭素原子を含む）から選ばれること
を特徴とする、上記のフッ化ビニリデンポリマーの製造
方法。 （２）酢酸アルキルが酢酸エチルであることを特徴とす
る、請求項１記載のフッ化ビニリデンポリマーの製造方
法。 （３）連鎖調節剤がモノマーに対して０．５〜３重量％
の割合で使用されることを特徴とする、請求項１または
２に記載のフッ化ビニリデンポリマーの製造方法。 （４）連鎖調節剤がモノマーに対して１〜２重量％の割
合で使用されることを特徴とする、請求項３記載のフッ
化ビニリデンポリマーの製造方法。 （５）開始剤がアルカリ金属ペルオキシジスルフェート
及びアンモニウムペルオキシジスルフェートから選ばれ
ることを特徴とする、請求項１記載のフッ化ビニリデン
ポリマーの製造方法。 （６）開始剤がアンモニウムペルオキシジスルフェート
であることを特徴とする、請求項５記載のフッ化ビニリ
デンポリマーの製造方法。 （７）触媒が水性相１ｌに対し０．００５ｇ〜０．５ｇ
の割合で使用されることを特徴とする、請求項１、５ま
たは６記載のフッ化ビニリデンポリマーの製造方法。 （８）開始剤及びフッ化ビニリデンが重合の過程中に仕
込み液に次第に導入されることを特徴とする、請求項１
〜７のいずれか一項記載のフッ化ビニリデンポリマーの
製造方法。（９）塗料の配合のための請求項１〜８のい
ずれか一項記載の方法により得られたフッ化ビニリデン
ポリマーの使用。 （１０）、金属のプレラッカー塗に意図される塗料の配
合のための請求項１〜８のいずれか一項記載の方法によ
り得られたフッ化ビニリデンポリマーの使用。[Scope of Claims] (1) A process for producing vinylidene fluoride polymers by discontinuous polymerization of vinylidene fluoride in an aqueous medium using peroxydisulfate as an initiator in the absence of an emulsifier, the method comprising: A regulator is introduced into the initial aqueous charge for polymerization, and the chain regulator is selected from alkyl acetates, the alkyl group containing from 1 to 3 carbon atoms. Method for producing vinylidene chloride polymer. (2) The method for producing a vinylidene fluoride polymer according to claim 1, wherein the alkyl acetate is ethyl acetate. (3) Chain regulator: 0.5 to 3% by weight based on monomer
The method for producing vinylidene fluoride polymer according to claim 1 or 2, characterized in that the vinylidene fluoride polymer is used in a proportion of . (4) The method for producing a vinylidene fluoride polymer according to claim 3, wherein the chain regulator is used in an amount of 1 to 2% by weight based on the monomer. (5) The method for producing a vinylidene fluoride polymer according to claim 1, characterized in that the initiator is selected from alkali metal peroxydisulfates and ammonium peroxydisulfates. (6) The method for producing a vinylidene fluoride polymer according to claim 5, wherein the initiator is ammonium peroxydisulfate. (7) Catalyst is 0.005g to 0.5g per liter of aqueous phase
7. The method for producing vinylidene fluoride polymer according to claim 1, 5 or 6, characterized in that the vinylidene fluoride polymer is used in a proportion of . (8) Claim 1, characterized in that the initiator and vinylidene fluoride are gradually introduced into the charge during the course of polymerization.
8. The method for producing vinylidene fluoride polymer according to any one of 7 to 7. (9) Use of the vinylidene fluoride polymer obtained by the method according to any one of claims 1 to 8 for the formulation of paints. (10) Use of vinylidene fluoride polymers obtained by the process according to any one of claims 1 to 8 for the formulation of coatings intended for pre-lacquering of metals.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8903497 | 1989-03-15 | ||
| FR8903497A FR2644466B1 (en) | 1989-03-15 | 1989-03-15 | PROCESS FOR THE MANUFACTURE OF VINYLIDENE FLUORIDE POLYMERS AND USE OF VINYLIDENE FLUORIDE POLYMERS FOR THE FORMULATION OF PAINTS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0328206A true JPH0328206A (en) | 1991-02-06 |
Family
ID=9379781
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2065514A Pending JPH0328206A (en) | 1989-03-15 | 1990-03-15 | Manufacture of vinyledene fluoride polymer and use of vinyledene fluoride polymer for blending paints |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5095081A (en) |
| EP (1) | EP0387938B1 (en) |
| JP (1) | JPH0328206A (en) |
| AT (1) | ATE94566T1 (en) |
| DE (1) | DE69003283D1 (en) |
| FR (1) | FR2644466B1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6383620B1 (en) | 1996-08-14 | 2002-05-07 | Daikin Industries, Ltd. | Antireflection article |
| WO2011030858A1 (en) | 2009-09-11 | 2011-03-17 | ダイキン工業株式会社 | Light-concentrating film, method for producing same, focusing element, solar cell, and focusing method |
| WO2012124728A1 (en) | 2011-03-14 | 2012-09-20 | ダイキン工業株式会社 | Light-gathering film and solar battery module |
| WO2013047827A1 (en) | 2011-09-30 | 2013-04-04 | ダイキン工業株式会社 | Light-condensing film, solar cell module, and transfer mold |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69207105T2 (en) * | 1991-08-01 | 1996-05-15 | Kureha Chemical Ind Co Ltd | Process for the preparation of vinylidene fluoride polymer |
| US5285002A (en) * | 1993-03-23 | 1994-02-08 | Minnesota Mining And Manufacturing Company | Fluorine-containing polymers and preparation and use thereof |
| IT1265033B1 (en) * | 1993-05-28 | 1996-10-28 | Ausimont Spa | HIGH MECHANICAL PERFORMANCE POLYVINYLIDENFLUORIDE AND HIGH THERMOCHEMICAL STABILITY, AND RELATED PREPARATION PROCESS |
| IT1265223B1 (en) * | 1993-11-25 | 1996-10-31 | Ausimont Spa | PROCESS FOR THE PREPARATION OF POLYMERS OF VINYLIDENFLUORIDE |
| JP3718850B2 (en) * | 1994-12-06 | 2005-11-24 | ダイキン工業株式会社 | Fluorine-containing elastic copolymer excellent in moldability, its production method and vulcanizing composition excellent in moldability |
| US6281280B1 (en) * | 1995-02-03 | 2001-08-28 | Ausimont Usa, Inc. | Low-gloss paints including polyvinylidene fluoride having a high melt viscosity |
| US5639837A (en) * | 1996-06-04 | 1997-06-17 | E. I. Du Pont De Nemours And Company | Process for making fluoropolymers |
| JP3818344B2 (en) * | 1997-11-20 | 2006-09-06 | 旭硝子株式会社 | Process for producing fluorine-containing aliphatic ring structure-containing polymer |
| US6649720B2 (en) | 2001-02-14 | 2003-11-18 | Atofina Chemicals, Inc. | Ethane as a chain transfer agent for vinylidene fluoride polymerization |
| FR2850387B1 (en) * | 2003-01-23 | 2005-03-04 | Atofina | PROCESS FOR PRODUCING PVDF |
| FR2852016B1 (en) | 2003-03-03 | 2006-07-07 | Atofina | PROCESS FOR PRODUCING THERMALLY STABLE PVDF |
| FR2852017B1 (en) | 2003-03-03 | 2005-04-22 | Atofina | PROCESS FOR PRODUCING THERMALLY STABLE PVDF |
| JP5655281B2 (en) * | 2008-06-10 | 2015-01-21 | 東ソー株式会社 | Chlorinated polyether and polyurethane comprising the same |
| FR2944285B1 (en) * | 2009-04-09 | 2011-11-25 | Francois Bauer | PROCESS FOR PRODUCING TERPOLYMERS BASED ON VDF, TRFE AND CFE OR CTFE |
| CN103459441A (en) * | 2011-03-31 | 2013-12-18 | 大金工业株式会社 | Method for producing fluorine-containing copolymer |
| KR101963637B1 (en) | 2011-07-15 | 2019-04-01 | 솔베이 스페셜티 폴리머스 이태리 에스.피.에이. | Aqueous vinylidene fluoride polymer latex |
| CN104497190B (en) * | 2014-12-29 | 2016-09-21 | 浙江孚诺林化工新材料有限公司 | A kind of preparation method of the partial fluorine ethylene polymer for lithium ion battery electrode material binding agent |
| CN106749798B (en) * | 2015-11-24 | 2019-03-22 | 浙江省化工研究院有限公司 | A kind of preparation method of coating type polyvinylidene fluoride polymer |
| CN106336476B (en) * | 2016-08-25 | 2019-12-10 | 浙江孚诺林化工新材料有限公司 | preparation method of vinylidene fluoride copolymer with high elongation at break |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2965595A (en) * | 1955-12-05 | 1960-12-20 | Du Pont | Process for polymerizing tetrafluoroethylene in the presence of polymerstabilizing agents |
| DE1072810B (en) * | 1955-12-05 | 1960-01-07 | E. I. Du Pont De Nemours And Company, Wilmington, Del. (V. St. A.) | Process for the polymerization or copolymerization of perfluorinated olefinically unsaturated compounds, especially of tetrafluoroethylene |
| US3032543A (en) * | 1959-02-04 | 1962-05-01 | Du Pont | Polymerization of tetrafluoroethylene |
| US3031437A (en) * | 1959-05-13 | 1962-04-24 | Pennsalt Chemicals Corp | Vinylidene fluoride polymers and copolymers |
| US3069401A (en) * | 1960-02-23 | 1962-12-18 | Du Pont | Copolymers of hexafluoropropylene vinylidene fluoride and aliphatic, chain transfer agents |
| DE1620989A1 (en) * | 1965-05-10 | 1970-07-09 | Montedison Spa | Process for the polymerization and copolymerization of vinyl fluoride |
| GB1149451A (en) * | 1967-04-10 | 1969-04-23 | Ici Ltd | Process for polymerising fluorinated monomers |
| US3640985A (en) * | 1969-05-16 | 1972-02-08 | Ppg Industries Inc | Polymerization of fluorine-containing ethylenically unsaturated monomers in the presence of a beta-hydroxyalkyl tertiary-butyl peroxide |
| BE754314A (en) * | 1969-08-05 | 1971-01-18 | Sueddeutsche Kalkstickstoff | PROCESS FOR PREPARING POLYVINYLIDENE FLUORIDE |
| US3739015A (en) * | 1970-09-04 | 1973-06-12 | Tanabe Seiyaku Co | Esters of p-phenoxy and p-alkoxy cinnamic acid |
| US3845024A (en) * | 1972-11-22 | 1974-10-29 | Du Pont | Continuous process for production of fluoroelastomers |
| FR2347389A2 (en) * | 1976-04-06 | 1977-11-04 | Du Pont | Vulcanisable fluorinated elastomer - which gives heat and solvent resistant prods. with good flexibility at low temp. |
| JPS5834484B2 (en) * | 1981-09-14 | 1983-07-27 | ダイキン工業株式会社 | Method for producing polyvinylidene fluoride powder |
| US4524197A (en) * | 1984-08-28 | 1985-06-18 | E. I. Du Pont De Nemours And Company | Process for making vinylidene fluoride containing fluoroelastomers |
| EP0176347B1 (en) * | 1984-09-24 | 1991-12-18 | AUSIMONT S.p.A. | Process for preparing vinylidene fluoride homopolymers and its copolymers |
-
1989
- 1989-03-15 FR FR8903497A patent/FR2644466B1/en not_active Expired - Fee Related
-
1990
- 1990-03-05 AT AT90200515T patent/ATE94566T1/en not_active IP Right Cessation
- 1990-03-05 DE DE90200515T patent/DE69003283D1/en not_active Expired - Lifetime
- 1990-03-05 EP EP90200515A patent/EP0387938B1/en not_active Expired - Lifetime
- 1990-03-07 US US07/489,493 patent/US5095081A/en not_active Expired - Fee Related
- 1990-03-15 JP JP2065514A patent/JPH0328206A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6383620B1 (en) | 1996-08-14 | 2002-05-07 | Daikin Industries, Ltd. | Antireflection article |
| WO2011030858A1 (en) | 2009-09-11 | 2011-03-17 | ダイキン工業株式会社 | Light-concentrating film, method for producing same, focusing element, solar cell, and focusing method |
| WO2012124728A1 (en) | 2011-03-14 | 2012-09-20 | ダイキン工業株式会社 | Light-gathering film and solar battery module |
| WO2013047827A1 (en) | 2011-09-30 | 2013-04-04 | ダイキン工業株式会社 | Light-condensing film, solar cell module, and transfer mold |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2644466A1 (en) | 1990-09-21 |
| FR2644466B1 (en) | 1992-08-14 |
| EP0387938B1 (en) | 1993-09-15 |
| DE69003283D1 (en) | 1993-10-21 |
| EP0387938A1 (en) | 1990-09-19 |
| US5095081A (en) | 1992-03-10 |
| ATE94566T1 (en) | 1993-10-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0328206A (en) | Manufacture of vinyledene fluoride polymer and use of vinyledene fluoride polymer for blending paints | |
| JP3298321B2 (en) | Aqueous dispersion of vinylidene fluoride-based copolymer, aqueous dispersion of vinylidene fluoride-based seed polymer and methods for producing them | |
| RU2411250C2 (en) | Using aqueous dispersions of vinylidene fluoride-based polymers to obtain paints for architecutural objects | |
| JP2715540B2 (en) | Aqueous dispersion, composite powder and organosol composition of fluorine-containing resin | |
| CA1336482C (en) | Treating an autodeposited coating with an alkaline material | |
| EP0295713B1 (en) | Gloss enhancement of autodeposited coatings | |
| JP4184442B2 (en) | Low crystallinity vinyl fluoride interpolymer | |
| JPS62109846A (en) | Aqueous dispersion of fluorine-containing copolymer particle and organosol composition of said particle | |
| CA1280843C (en) | Vinylidene chloride latex in autodeposition and low temperature cure | |
| JPH0657724B2 (en) | Crosslinkable fluorine-containing copolymer and use thereof | |
| Potisk et al. | Microemulsion polymerization of butyl acrylate. 1. Effect of initiator type and concentration | |
| KR100374781B1 (en) | Use for poly (vinylidene fluoride) mixtures and high gloss paint formulations | |
| US4562098A (en) | Water or steam cure of autodeposited resin coatings on metallic substrates | |
| DE2757065C2 (en) | Process for the polymerization of vinyl chloride, alone or together with other vinyl halides or other comonomers copolymerizable with vinyl chloride, in an aqueous dispersion and in a reaction vessel for carrying it out | |
| US4687708A (en) | High build fluorocarbon polymer dispersions and their preparation | |
| US3714137A (en) | PROCESS FOR THE PRODUCTION OF POLYVINYLIDENE FLUORIDE IN THE PRESENCE OF A PEROXYDISULFATE INITIATOR AT AN ACIDIC pH | |
| US3708463A (en) | Process for preparing vinylidene fluoride polymers for coating applications | |
| JPS5865711A (en) | Production of polyvinylidene fluoride powder | |
| JP3115954B2 (en) | Method for producing partially saponified polyvinyl alcohol | |
| JP3146842B2 (en) | Water-based paints composed of fluorinated copolymers | |
| JPH0618889B2 (en) | Method for producing vinyl fluoride-containing aqueous dispersion | |
| JPS6320442B2 (en) | ||
| JPS5834814A (en) | Polymerization of vinylidene fluoride | |
| JPH11166007A (en) | Production of fluorine-containing copolymer aqueous dispersion | |
| US4476286A (en) | Thermosetting cationic latex compositions containing aminoplast curing agents |